CA1330134C - Finely divided gelled polymer and process for producing the same - Google Patents
Finely divided gelled polymer and process for producing the sameInfo
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- CA1330134C CA1330134C CA000607733A CA607733A CA1330134C CA 1330134 C CA1330134 C CA 1330134C CA 000607733 A CA000607733 A CA 000607733A CA 607733 A CA607733 A CA 607733A CA 1330134 C CA1330134 C CA 1330134C
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- monomer
- finely divided
- group
- gelled polymer
- divided gelled
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A finely divided gelled polymer obtained by emulsion polymerizing (a) a polymerizable monomer containing at least two radically polymerizable unsaturated groups in the molecule, and (b) a radically polymerizable unsaturated monomer other than the one mentioned in (a), above in the presence of a reactive emulsifier containing an allyl group in the molecule.
A process for producing a finely divided gelled polymer which comprises emulsion polymerizing (a) a polymerizable monomer containing at least two radically polymerizable unsaturated groups in the molecule, and (b) a radically polymerizable unsaturated monomer other than the one mentioned in (a), above in the presence of a reactive emulsifier containing an allyl group in the molecule, characterized by using a water-soluble azoamide compound as a polymerization inintiator.
A finely divided gelled polymer obtained by emulsion polymerizing (a) a polymerizable monomer containing at least two radically polymerizable unsaturated groups in the molecule, and (b) a radically polymerizable unsaturated monomer other than the one mentioned in (a), above in the presence of a reactive emulsifier containing an allyl group in the molecule.
A process for producing a finely divided gelled polymer which comprises emulsion polymerizing (a) a polymerizable monomer containing at least two radically polymerizable unsaturated groups in the molecule, and (b) a radically polymerizable unsaturated monomer other than the one mentioned in (a), above in the presence of a reactive emulsifier containing an allyl group in the molecule, characterized by using a water-soluble azoamide compound as a polymerization inintiator.
Description
FINELY DIVIDED GELLED POLYMER AND PROCESS -FOR PRODUCING THE SAME
This invention relates to a finely divided gelled polymer and a process for producing the same. More specifically, this invention relates to a finely divided gelled polymer crosslinked internally obtained by emul-sion polymerization in the presence of a reactive emulsi-fier, a cationically electrodepositable polymer crosslink-ed internally having a hydrolyzable alkoxy silane group and a hydroxyl group, obtained by emulsion polymerization in the presence of a reactive emulsifier, and a process for producing a finely divided gelled polymer excellent in polymerization stability comprising carrying out emulsion polymerization in the presence of a water-soluble azoamide compound as a polymerization initiator.
tPrior art]
Finely divided polymers gelled by crosslinking reactions in the particles and processes for producing such polymers have heretofore been well known. For -example, there have been known a process for emulsion polymerizing a monomeric mixture comprising a monomer for -~
crosslinking containing at least two ethylenic double bonds in an aqueous medium (British Patent No. 967,051 -i ; and European Patent Application No. 259181-A) and a ~ -process for obtaining a polymer comprising dispersion polymerizing a monomeric mixture containing glycidyl (meth)acrylate and (meth)acrylic acid in the presence of ~; a dispersion stabilizer in a non-aqueous medium, and simultaneously, reacting these functional groups (U.S.
Patent 4,025,473). Especially, as processes for produc-ing a polymer in an aqueous medium using an alkoxy silane monomer, there may be cited a process for obtaining a polymer comprising emulsion polymeriaing a mixture of an alkoxy silane monomer with the other monomer in an aqueous medium in the presence of a non-reactive surface active agent (Europen Patent Application No. 153600-A), a -process for obtaining a delustered electrodeposition- -- ~ - . ' : ' ' - ':
.
coated film for aluminum building material which com-prises copolymerizing an alkoxy silane monomer, (meth)-acrylic acid and the other monomer, dispersing the result-ing copolymer in water, and then subjecting the disper sion to electrodeposition coating. (Japanese Laid-Open Patent Publication No, 67396/1984), a water-soluble composition comprising combining an acryl copolymer containing an alkoxy silane group and a carboxyl group with a colloidal silica (Japanese Patent Publication No.
47178/1986) and a process for obtaining a polymer com-prising dispersing an acryl copolymer containig an alkoxy silane group and a cationic group in water and crosslink- -ing the resulting dispersed copolymer in the molecule -(European Patent Application No. 282000-A).
The finely divided gelled polymers obtained by the conventional processes are added to a paint composi- ~ ~
tion, exert influences over the rheological characte- -ristics and physical characteristics of the paint composi- ~ ;
tion, resulting in contributing to the improvements in the spraying effect of the paint, prevention of sagging of the coated film and the pattern control of a metallic pigment. However, many of such finely divided gelled - -polymers are of non-aqueous dispersion, or even if they - -~
are dispersed in aqueous medium, they are dispersions obtained by emulsion polymerization in the presence of a non-reactive surface active agent, and adversely affect various properties of the coated film such as water resistance, solvent resistance and chemical resistance.
On the other hand, cationically electrodeposit- ;
able paints broadly used in various industries centering around the automobile industry has per se excellent rust-inhibiting property, however, the coated film in the edge portion of the object to be coated do not become thick and are inferior in edge covering property. In order to solve this problem, investigations were made in an attempt to apply said finely divided gelled polymer to . ~ , ~ ~330134 the cationically electrodepositable paint. Since the A known finely divided gelled polymers are dispersions of ~-1~ anionic or nonionic or nonionic type, it is usually difficult to apply them to cationically electrodeposit able paint. Even if the known finely divided gelled polymers can be applied to the cationically electrodeposit-able paint, the stability of the electrodeposition coat-ing bath, electrodepositable characteristics, as well as water resistance and corrosion resistance of the coating are impaired. Consequently, a cationically electrodeposit-able paint containing the known finely divided gelled polymers cannot be applied to the practical uses in this field.
The present inventors have made assiduous lS investigations to develop a finely divided gelled polymer which would be useful as a vehicle for a paint, and found as a result that a finely divided gelled polymer cross-linked internally incorporated with a group having a surface activity by chemical bond in the surface of the resin is very effective for solving ~ drawback. This finely divided gelled polymer has a good dispersion stability, and when added to a paint, it is very effective for improving the rheological characteristics and physical characteristics of the paint composition without adversely affecting the various properties of the coated film such as water resistance, solvent resistance and chemical resistance.
Further, the present inventors found that a finely divided gelled polymer crosslinked internally hav- ~ `-ing an alkoxy silane goup, a hydroxyl group and a cationic ; group is useful as a rheology controlling agent of a cationically electrodepositable paint. This polymer has ~
a cationic electrodepositability, does not impair stabil- ~ -ity of the electrodeposition coating bath and electro~
depositable characteristics even when it is added to a cationically electrodepositable paint, does not impair ;~
: ~:, . .
1 330 1 34 ~ -the water resistance, corrosion resistance and smoothness of the surface of the coated film because of crosslinking between particles and crosslinking between the polymer particles with the base resin derived from condensation -, 5 of a silanol group formed by the hydrolysis of alkoxy -- - -silane group with another silanol group and a hydroxyl group at the time of baking , and is very effective for prevention of the cissing and improvement of the edge -~ -cover property, the adhesivility and the chipping resis-10 tance of the cationically electrodeposited coated film. : -And this finding has led us to completion of this inven-tion. -Thus, according to one aspect of this inven- ~ ;
tion, there is provided a finely divided gelled polymer which is obtained by emulsion polymerizing (a) a polymerizable monomer having at least two - --radically polymerizable unsaturated groups in the mole-cule and --(b) a radically polymerizable unsaturated monomer other than the one mentioned in (a) above in the presence of a reactive emulsifier having an allyl group in the molecule. ;
And, according to another aspect of this in-vention, there is provided a process for producing a -finely divided geled polymer excellent in polymerization stability which comprises emulsion polymerizing Z ~;
(a) a polymerizable monomer having at least two -radically polymerizable unsaturated groups and (b) a radically polymerizable unsaturated ~ -monomer other than the one mentioned in (a) above in the presence of a reactive emulsifier having an allyl group in the molecule, characterized by using a water-soluble azoamide compound as a polymerization initiator.
Hereinbelow, a further detailled description will be made with reference to a finely divided gelled polymer and a process for producing the same according to this invention.
In this invention, the monomers constituting the finely divided gelled polymer are (a) a polymerizable monomer having at least two radically polymerizable unsaturated groups in the mole-cule, and (b) a radically polymerizable unsaturated monomer other than the one mentioned in (a) above.
The polymerizable monomer having at least two ~10 radically polymerizable unsaturated groups-rn~~aeF~(a) [hereinafter referred to as "the monomer (a)~] includes a polymerizable un~aturated monocaboxylic acid ester of a polyhydric alcohol, a polymerizable unsaturated alcohol -ester of a polybasic acid and an aromatic monomer substi-tuted with at least two vinyl groups.
Specific examples of the monomer (a) include ethylene glycol diacrylate, ethylene glycol dimetha- ~ - -crylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethac- - ~- -20 rylate, trimethylolpropane triacrylate, trimethylol- - --~
propane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacry-late, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate, glycerol diacrylate, glycerol allyloxy dimethacrylate, l,l,l-trishydroxymethylethane diacrylate, l,l,l-trishydroxy-methylethane triacrylate, l,l,l-trihydroxymethylethane 3Q dimethacrylate, l,l,l-trishydroxymethylethane trimeth- -;;
acrylate, l,l,l-trishydroxymethylpropane diacrylate, l,l,l-trishydroxymethylpropane triacrylate, l,l,l-trishydroxymethylpropane dimethacrylate, l,l,l-trishydroxymethylpropane trimethacrylate, triallyl cyanurate, trially isocyànurate, trially trimellitate, -diallyl terephthalate, diallyl phthalate and divinyl benzene.
~ .: .:. : . . :
'.. ~ '. -~.''' ','; '' ' 1 330 1 34 ~; -,.
- 6 - ;
Of the aforesaid monomers (a), the polymeriz- -able unsaturated monocarboxylic acid ester of a poly-hydric alcohol and the aromatic monomer substituted with at least two vinyl monomers are preferable for this 5 invention. Of these, ethylene glycol di(meth)acrylate, ~ ;
triethylene glycol dimethacrylate, tetraethylene glycol ;
dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate and divinyl benzene are espe- ~ ~ -cially preferable.
_ The radically polymerizable unsaturated monomer A f oaid (b) lhereinafter referred to as "the monomer (b)~] is another half of the monomers constituting the finely divided gelled polymer of this invention, which includes the monomers belonging to the following groups.
A poly~erizable unsaturated vinyl silane ;~
monomer containing a vinylic double bond and a hydro-lyzable alkoxy silane group: -For example, a compound represented by the -20 general formula ; - -R3SiX.
In the formula, X represents a vinylic unsatu-rated group such as gamma-methacryloxypropyl and R re-presents an acetoxy group or an alkoxy group having 1 to 8 carbon atoms. Examples of the alkoxy group include besides methoxy, ethoxy, propoxy, butoxy, isobutoxy, pentoxy and hexoxy; methoxymethoxy, ethoxymethoxy, alkoxyallyloxy and ethoxyphenoxy. The preferable R is a methoxy or ethoxy group.
Typical examples of the monomer include vinyl ~
trimethoxysilane, vinyltriethoxysilane, vinyltris(2- ~ ; -methoxyethoxy)silane, gamma-methacryloxypropyl tri- ;
methoxysilane and vinyl triacetoxysilanes. Of these, the most preferble is gamma-methacryloxypropyl trimethoxy-silane.
A polymerizable unsaturated monomer containing a vinylic double bond and a hydroxyl group: -`~
For example, there may be cited 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, allyl alcohol and methallyl alcohol.
A polymerizable unsaturated monomer containing a carboxyl group:
For example, there may be cited acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid.
A nitrogen-containing alkyl (meth)acrylate monomer For example, there may be cited dimethyl amino~
ethyl (meth)ecrylate.
A polymerizable unsaturated amide monomer: ~ -For example, there may be cited acrylamide ~ -15 methacrylamide, N,N-dimethylacrylamide and N,N-dimethyl- ~ ~;
amino propyl acrylamide.
A polymerizable unsaturated nitrile monomer:
For example, there may be cited acrylonitrile ~ -and methacrylonitrile. ; ~-An alkyl (meth)acrylate monomer;
For example, there may be cited a (Cl-C4) alkyl ester of (meth)acrylic acid such as methyl (meth)- - -~
acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and lauryl (meth)acrylate.
A polymerizable unsaturated glycidyl monomer:
For example, there may be cited glycidyl (meth)- -;~ acrylate, A polymerizable vinyl aromatic monomer:
For example, there may be cited styrene, alpha-~, 30 methyl styrene, vinyl toluene and t-butyl styrene. -~
An alpha-olefin monomer: ~ - ; 'r' ' For example, there may be cited ethylene and propylene. -An aliphatic vinyl ester monomer:
For example, there may be cited vinyl acetate and vinyl propionate.
: -: .
,, ~
. ~ - .: .: :
A diene monomer; ~ ;
For example, there may be cited butadiene and isoprene.
These monomers (b) may be properly selected 5 according to the desired characteristics of the finely -divided gelled polymer and may be used singly or in combination of at least two.
The blending ratio of the monomer (a) and the monomer (b) constituting the finely divided gelled polymer of this invention is within the following range.
The monomer (a): 1 to 99% by weight, preferably 3 to 20~ by weight -The monomer (b): 1 to 99% by weight, preferably 80 to 97% by weight.
Further, in this invention, a cationic finely divided gelled polymer which is especially useful as a rheology controlling agent for a cationic electrodeposit-able paint may be obtained by emulsion polymerizing the aforsaid monomer (a) and the following (b-l), (b-2) and (b-3) monomers selected from the aforesaid monomer (b) as the essential components in the presence of a cationic reactive emulsifier containing an allyl group in the molecule.
b-l) a polymerizable unsaturated vinylsilane monomer containing a vinylic double bond and a hydrolyzable alkoxysilane group~
(b-2) a polymerizable monomer containing a vinylic double bond and a hydroxyl group;
and ~ ~ -~, ~ 30 (b-3) the other polymerizable monomer having no carboxyl group selected from the group ; consisting of a nitrogen-containing alkyl (meth)acrylate monomer, a polymerizable unsaturated amide monomer, a polymer-izable unsaturated nitrile monomer, an alkyl ~meth)acrylate monomer, a polymer-': :
~ . .
^ 1 330 1 34 _ 9 _ izable unsaturated glycidyl monomer, a -~
polymerizable vinyl aromatic monomer, an ;~-~
alpha-olefin monomer, a diene monomer and vinyl ester monomer of a fatty acid.
The blending ratio of the monomer (a) and the (b-l) to (b-3) monomers is within the following range.
The monomer (a): 1 to 30% by weight, preferably 3 to 20% by weight; -~
The monomer ~b-l): 1 to 30% by weight, preferably 3 to 20% by weight;
The monomer (b-2): 1 to 30% by weight, preferably -3 to 20% by weight;
The monomer (b-3): 10 to 97% by weight, preferably 40 to 91% by weight. ~ -lS As the reactive emulsifier containing an allyl group in the molecule used in this invention, the fol~
lowing compounds are included.
A (1) An allYl qrouP-containinq anionic reactive emulsifer;
-~ As typical ones, there may-e-cited a sulfonic acid salt represented by the following general formula 1) or (2) `~ ln-coo~Ao~ncn2-c-cn2 (1) ~:~
CH-COO( AO) nCH2-C-CH
CH-COOR2 (2) ;- ~
;, S03Ml , ~, ,, wherein Rl represents a hydrogen atom or a methyl group, R2 represents a hydrocarbon having a hydrocarbon group or a substituent, or an ; `` --:. :: . . ::~
-~ 1 330 1 34 -- 1 0 -- " "
organic group containing an oxyalkylene group, ; .
A represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, n is 0 or a positive number, M represents an alkali metal or alkaline earth metal, ammonium, an organic amine salt group or an organic quaternary ammonium salt group, and m is a -:
atomic or ionic valence of M;
or a sulfosuccinic acid diester salt represented by the -following general formula 3 or 4 .~
CIH2COO(AO)nRl R12 CHCOO-CH2CHCH20CH2C=CH2 (3) OH
3Ml m CH2CoO-CH2Cl HcH20cH2c CH2 OH
CHCOO(AO)nRl (4) S03Ml m wherein Rl represents a hydrocarbon group optionally :~ having a substituent, a phenyl group, an amino group or a carbocylic acid residue, R2 re-presents a hydrogen atom or a methyl group, A ~.
represents an alkylene group having 2 to 4 carbon atoms, n is an integer of 0 to 100, M - :¦
represents a univalent or divalent cation, and m is an ionic valence of M;
: or a compound represented by the following general formula (5) . ~ ~ -R
~ -O(AO)nSO3M (5) R2 ~ :
1 3 3 0 1 3 4 ! ~ ~
-- 1 1 -- ~ , wherein Rl represents an alkyl, alkenyl or aralkyl - -group having 4 to 1~ carbon atoms, R2 repre-sents a hydrogen atom or an alkyl an alkenyl or ~ ~;
an aralkyl group having a 4 to 18 carbon atoms, A represents an alkylene group having 2 to 4 - -carbon atoms or a substituted alkylene group, n is an integer of 2 to 200 and M represents an -alkali metal atom, NH4 or an alkanolamine residue.
These compounds are known (see, for example, Japanese Patent Publication No. 46291/1974, DE 3317336-A, Japanese Laid-Open Publication No. 221431/1987 and Japanese Laid-Open Patent Publication No. 23725/1988). -' ~hese compounds are commercially available ~ under ther~LJ~ o~ nEliminol JS-2" (Sanyo Chemical - ~
;~ Industries, Ltd.), "Ratemuru S Series~ (Kao Corporation) - - -and ~Aqualon HS Series~ (Dai-ichi Rogyo Seiyaku Co., :
Ltd.).
Of the aforesaid emulsifiens, an anionic re~
~` active emulsifier which is gradually incorporated in the polymer during the polymerization is suitable, and espe-cially so long as it is an anionic reactive emulsifier ; con~aining an allyl group which is a group relatively low ;
in reactivity, it is not limited to what is mentioned above only, but it is included within a broad range. And'`~
the æmount of the anionic reactive emulsifier containin~
thè allyl group used is usually 0.1 to 30% by weight, ;~ preferably 0.5 to 5% by weight per 100 parts by weight of lthe solids content of the finely divided gelled poly-mer.
-~ (2) An allyl group-contalnlng catlonic reactlve emulsifier~
A typical example is a reactive emulsifier having a quaternery ammonium salt represented by the `~ following general formula (6) ~ ~
,' :''.~'` ' ' 1 N CH2-CH-CH2-O-CH2-1=CH (6) ~ :
' wherein Rl represents a hydrocarbon group having 8 to 22 carbon atoms optionally having a substituent, .
R2 and R3 represent an alkyl group having 1 to 3 carbon atoms, R4 represents a hydrogen atom or a methyl group and X~ represents a univalent anion.
This compound is known (see Japanese Laid-Open Patent Publication No. 78947/1985) and is commercially A available under the traden~me of "Ratemuru K-180" (Kao -Corporation).
Of the aforesaid emulsifiers, a cationic re- ..
active emulsifier which is gradually incorpotated in the .
polymer during the polymerization is suitable, and if it is a cationec reactive emulsifier containing an allyl . ~ ::
group which is a group relatively low in reactivity, it is not limited to what is mentioned above only, but -included within a broad range. The amount of the allyl . - :~
20 group-containing cationic reactive emulsifier used is :
usually 0.1 to 30% by weight, preferably 0.5 to 5% by :
weight per 100 parts by weight of the solids content of the finely divided gelled polymer.
~: ~3) An allYl qrouP-containinq nonionic reactive emulsifier:
What is typical of this category is a compound represented by the following general formula (7) CH CH=CH ..
Rl~,~_~
~ O ~-O(AO)nH (7) R ~ :
.
!; `' :. : - , . - ' , ~ . , .. .. , . , . , - : : : . , , :: . ' - . . - ' : . ' , ., - . , . .: . :- : :' ; . . : . . ; -- . ....
1 3 3 0 1 3 4 ! ~ ~
wherein -~
Rl represents an alkyl, alkenyl or aralkyl -~
group having 4 to 18 carbon atoms, R2 represents ; -~
a hydrogen atom, an alkyl group, alkenyl group or aralkyl group having 4 to 18 carbon - atoms, A represents i~ alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and n is an integer of 2 to 200. -This compound is known (see Japanese Laid-Open 10 Patent Publication No. 100502/1087) and commercially available under the trade ~e~of "H-3355N" (Dai-ichi Rogyo Seiyaku Co., Ltd.), Of the aforesaid emulsifiers, a nonionic reac-tive emulsifier which is gradually incorporated in the 15 polymer during the polymerization is suitable, and if it ~- --is a nonionic reactive emulsifier containing an allyl group which is a group relatively low in reactivity, the emulsifier is not limited to what is mentioned above only, but is included within a broad range. In addition, -20 this nonionic reactive emulsifier may be blended at an -optional ratio with the anionic reactive emulsifier or ~-the cationic reactive emulsifier, and the blending ratio -is properly selected according to the desired characte~
ristics of the finely divided gelled polymer. `;~
~he amount of the mixture of the anionic re- ~ - ~
active emulsifier or the cationic reactive emulsifier -~ -with the nonionic reactive emulsifier used is usually 0.1 to 30% by weight, preferably 0.5 to 5% by weight per 100 parts by weight of the solids content of the finely - -30 divided gelled polymer. ` ~ ~ `
As a polymerization initiator used in this~ -~
invention, a water-soluble azoamide compound represented by the following general formula (8) .: . .. .: ..
IH3 ICH3 ;~
HO-X-NH-C-C-N-N-C - C-NH-X-OH (81 ~ .
Il I I ... ,'' :'. ''.
.`';.'''"'''- ' "' -. ...
wherein X represents a linear-chain or branched-chain alkylene group having 2 to 12 carbon atoms, or represented by the following general formula t9) - -X CH2 7H3 ICH3 I H2X :.
X CH2-C-HN - C-C-N=N - C - C_NH_C_CH2X (9) wherein at least one of Xl, X2, X3 represents a hydroxyl group and the remaining represents a hydrogen atom, is especially suitable.
_ This compound is known (see Japanese Laid-Open A Patent Publications Nos. 218618/1986 and 63643/1986) and is commercially available under the trade namo of "VA
Series" (Wako Pure Chemicals Industries, Ltd,).
The amount of the polymerization initiator may be usually within the range of 0.1 to 1.5 parts by weight per 100 parts by weight of the solids content of the finely divided gelled polymer.
Copolymerization of the unsaturated monomers 20 (a) and (b) may be carried out by the known process for ;
emulsion polymerization, viz. a process for producing an -acryl copolymer. A mixture of the monomers may be re-acted in the presence of a polymerization initiator of a water-soluble azoamide com2ound at a reaction temperature of usually about 50C to about 100C, preferably about ` 80C to about 95C for about 1 to about 20 hours, -The finely divided gelled polymer of this invention has a solids resin content of usually about 10 to about 40% by weight based on the total amount of its aqueous dispersion. The particle diameter of the finely divided gelled polymer is less than 500 nm, preferably 10 to 300 nm, more preferably 50 to 100 nm. The particle ~ `
diameter can be adjusted by adjusting the amount and/or the ratio of the amount of the reactive emulsifier having an allyl group in the molecule, and a finely divided gelled polymer having a particle diameter within the desired range can be easily obtained.
The finely divided gelled polymer of this invention is characterized in that the degree of cross-linking and the hardness thereof can be optionally control-led. When the hardness is low, by air drying, the parti-cles are mutually fused to form a continuous coated film,whereby the coated film large in the initial modudlus and rich in flexibility can be formed. And when the hardhess ; -and the crosslinking density become high, the trans-parency of the polymer film deteriorates, and many streaks and cracks are brought about, but it i8 possible to form a uniform, flat coated film by the joint use of a `
A coalescing agent or ra~i~sin~ ~he drying temperature.
The finely ~YnrhhK~gelled polymer of this invention can be used per se as a vehicle of an emulsion 20 paint that forms a coated film. Further, since it possess- ~ -es hydroxyl groups effectively introduced into the polymer by chemical bonding from a water-soluble azoamide compound which is used as a polymerization initiator, the polymer `~
may also be used as a material for an aqueous baking ~-~ :~
25 paint to be baked and hardened in admixture with an ~ --aminoplast resin such as methylolated melamine resin.
And, when the finely divided gelled polymer is -powderized and added to a powder paint, the polymer -~
particles are useful for improving the blocking property ; -30 and the physical properties of the coated film, and in : -addition, when dispersed in an aqueous solvent, it re- -mains as primary particle and is less viscous. According-ly, it is useful as a material for a high-solid type paint as well. ~esides, it is possible to mix the polymer 35 with the solvent type paint, water-soluble paint and ~-emulsion paint and use it for improving the properties of such paints.
A cationically electrodepositable finely divid-ed gelled polymer obtained by this invention, when added to ordinary cationecally electrodepositable paint and co-electrodeposited, does not bring about such problems as agglomeration, abno~mal electrodeposition and sedimen-tation, and plays a role of a flow controller at the time when the electrodeposited coated film is thermally harde-ned, and exhibits an excellent cissing inhibiting effectand the edge covering effect. Again, the coated film forms a microseparating structure and brings about a large improving effect of the physical properties of the coated film.
~he reason why the finely divided gelled polymer is stably produced by the emulsion polymerization process ~ of this invention is not necessarily c~ear at this point A Of timing. However, it is ~ sler ~ sttributable to the bec~ c~s~ ¢o~O c,~ d fact that bccouso-a water-soluble azoamide ~ompount-used 20 as a polymerization initiatior is a very useful polymer- ~ -~
ization initiator for an emulsion polymerization at a relatively high-temperature, even under the polymeriation conditions at a relatively high temperature of from about 80C to about 95C, the coagulation of th$ produced finely divided gelled polymers is ingibitcd, and that a grou~ having a surface activity is incorporated in the pos60foaionl0f hydroxyl groups effectively introduced to the surface of the polymer by chemical bonding, and that due to thc pPo33c~sion of hydroxyl groups effectively introduced to the surface of the polymer by chemical bonding from water-soluble azoamide compound as the polymerization initiator, the affinity of the polymer with water which is a continuous phase is very good, which enables the polymer to be stably present in water.
The following examples will more specifically illustrate this invention. All parts and percentages appearing in the following examples are by weight.
EXAMPLES 1 to 10 A 1-liter flask o~uppo~ with a stirrer, a thermometer, a condensing pipe and a heating mantle was -charged with deionized water in amounts shown in Table-l and the emulsifiers shown in Table-l in amounts shown in Table-l, and the contents were heated with stirring to 90C, to which 20% of aqueous solutions of 12.5 parts of -the polymerization initiator shown in Table-l dissolved in 500 parts of deionized water was added. After 15 minutes since the addition, 5% of the monomeric m~cture shown in Table-l was added. Then, after further stirring for 30 minutes, the remaining monomeric mixtures and the polymerization initiator began to be added dropwise. The - -monomeric mixtures and the polymerization initiators were - -~
15 added dropwise over 3 hours and 3.5 hours, respectively. - -~
During the period, the polym~rization temperature was -- -maintained at 90C. After dropping of the aqueous solu-tions of the polymerization initiators, heating~ Y~
continued for 30 minutes to maintain the temperature at ~ ` -90C, then the temperature was lowered to room tempera-ture. The resulting polymers were taken out using a ~
filter cloth ~ obtain finely divided gelled polymers ~ - -having the solids content of 20%. The properties of the -resulting polymers are shown in Table-2. ~
COMPARATIVE EXAMPLE 1 - `
Example 1 was repeated except that the charged ~ -contents of the l-liter flask were changed to 3543.1 parts of deionized water and 44.4 parts of an anionic ~ `
reactive emulsifier of "Newcol 271A" (trade namc Nippon Nyukazai Co., Ltd., a 45% aqueous solution) to obtain a finely divided gelled polymer having the pro-perties shown in Table-2. ~ -;
When emulsion polymerization was carried out as in Example 1, except that the charged contents of the l-liter flask w changed to 3567.5 parts of deionized water and 20 parts of an anionic vinylic reactive emul-sifier of sodium p-styrenesulfonate, while the monomers werer being added dropwise, the system agglomerated and a finely devided gelled polymer was not obtained.
When emulsion polymerization was carried out as in Example 1 except that the charged contents of the l-liter flask were changed to 3567.5 parts of deionized water and 20 parts of an oligoester acrylate type anionic reactive emulsifier of "Newfrontire A-229E" (trade name 10 ~ Dai-ichi Kogyo Seiyaku Co., Ltd.), while the monomers were being added dropwise, the system agglomerated and a finely divided gelled polymer was not obtained.
According to the same prescription as in Ex-15 ample 7 except that the charged contents of the l-liter flask were changed to 3555.8 parts of deionized water and a cationic non-rçactive emulsifier of "Kotamine 86P Conc~ `
(tradc~m~ of stearyl trimethyl ammonium chloride of Kao Corporation, a 63~ aqueous solution), a finely divided 20 gelled polymer having properties shown in Table-2 was obtained.
When emulsion polymerization was carried out according to the same prescription as in Example 7 except -25 that the polymerization initiaor was changed to a water-soluble azodiamidine compound of ~V-50" (2,2'-axobis(2-methylpropionamidine)dihydrochloride, a product of Wako -~
;- ~ Pure Chemicals Industries, Ltd.), while the monomers were --being added dropwise, the system agglomerated, and a ~ ``-, 30 finely divided gelled polymer was not obtained.
; COMPARATIVE EXAMPLE 6 ~ f ; According to the same prescription as in Example 6 except that the following mixture of monomers was used as the monomeric mixture, a finely divided gelled polymer 35 having properties shown in Table-2 was obtained. ~ -Styrene 500 parts n-Butyl acrylate 500 parts ~ 3301 34 -- 1 9 , Table-l .
¦Amount of ¦initially Emulsifier Icharged deionized -\ water Kind *1 Amount *2 (parts) used (parts) __ ,' . ,' ' . .
1 3536.5 JS-2 51(20) 2 3547.5 S-120A 40(20) 3 3547.5 S-120A 40(20) 4 3567.5 HS-10 20(20) 3557.5 S-120A/H-3355N 20/10(10/10) 6 3507.5 R-180 80(20) 7 3507.5 K-180 80(20) ;
8 3507.5 X-180 80(20) -9 3517.5 X-180 120(30) 3562.5 K-180/H-3355N 60/15(15/15) 1 3543.1 N-271A 44.4(20) 2 3567.5 Sodium p-styrenesulfonate 20(20) ~-~ 3 3567.5 A-229E 20(20) .~4 3555.8 86P 31.7(20) 3507.5 X-180 80(20) 6 3507.5 K-180 80(20) - to be continued -~ 133013~ ~
Table-l (continued) Monomer Kind of polymeri-Cbmposition *3 Amount zation used (parts) *4 1 St/nBA/1.6-HDDA 470/470/60 VA-086 2 St/nEA/1,6-HDDA 470/470/60 VA-086 3 St/nBAJl,6-HDDAv~Ea/MoaC 450/450/60/20/20 VA-086 4 St/neA~1,6-HDDA 470/470/60 VA-086 5 St/nBA/1,6-HDDA 470/470/60 VA-086 ~ 6 St/nBA/1,6-HDDA 470/470/60 VA-086 X 7 St/nB~/1,6-HDDA/HEP/K~M-503 430/440/40/40/50 VA-086 8 St/ne~/1,6-~HDDA/bEa/YæX-503 430/440/40/40/50 VA-080 9 MM~/nB~/1,6-HDDA 470/470/60 VA-086 O MM~nB~/1,6-HDDA 470/470/60 VA-086 1 St/nB~/l,6-HDDA 470/470/60 VA-086 X 2 St/nEA41,6-HDDA 470/470/60 VA-086 P 3 St/nBA/1,6-HDDA 470/470/60 VA-086 4 St/nBA/1,6-HDDAvHEa/Y~M-503 430/440/40/40/50 VA-086 5 St/n2~/1,6-HDDAvEEAv~M-503 430/440/40/40/50 V-50 6 St/nB~ 50/50 VA-086 .'.'~ ~ '' '.-.~
(NOTE) in Table-l *1 JS-2: An allyl group-containing anionic r~actdive A emulsifier of a sulfosuccinic acid type ~ ~ -"Eleminol JS-2" of Sanyo Chemical Industries, Ltd., a 39% aqueous solution), S-120A: an allyl group-containing anionic reactive emulsifier of a sulfo-succinic acid type (t ~ namc "Ratemuru S-120A of Xao Corporation, a 50% aqueous solution), HS-10: an ;
allyl group-containing anionic reactive emulsifier of a sulfonic acid type (trade ~ 'Aqualon HS-10"
of Dai-ichi Kogyo Seiyaku Co., Ltd., a 100% net -;
product), H-3355N: an allyl group-containing nonio-nic reactive emulsifier (a product of Dai-ichi Kogyo Seiyaku Co., Ltd., a 100% net produc ~ , K-180: an allyl group-containing cationic reactive emulsifier of a quaternary ammonium salt type (trade ~
"Ratemuru K-180" of Kao Corporation, a 25% aqueous solution, N-271A: an anionic non-reactive emulsifier of a sulfonic acid type ~trr~4ddcen~mmcr~nNewcol 271A f Nippon Nykazai Co., Ltd., a 45% aqueous solution), A-229E: an anionic reactive emulsifier of an oligo-ester acrylate type (trade n~mP "Newfrontier A-229E, -a 100% net product). --*2 Numerals inside the brackets show the amounts used calculated as the solids contents.
*3 St; styrene, n-BA; n-butyl acrylate, 1,6-HDDA;
1,6-hexanediol diacrylate, HEA; 2-hydroxyethyl acrylate, MAAc; methacrylic acid, KBM-503; gamma-methacryloxypropyltrimethoxy silane, procuced by Shin-Etsu Chemical Co., Ltd. and is commercially available, MMA; me~hyl methacrylate. -;~
s~
*4 VA-086; a water-*e~ ~ ~azoamide polymerization initiator: 2,2'-azobis[2~methyl-N-(2-hydroxyethyl)-propionamide] produced by Wako Pure Chemicals Industries, Ltd. and is commercialy available, VA-080; a water-soluble azoamide polymerization initiator; 2,2'-azobis{2-methyl-N-[l,l-bis-thydroxymethyl)-2-hydroxyethyl3propionamide}, pro-duced by Wako Pure Chemicals Industries, Ltd., V-50 a water-soluble azoamidine polymerization initiator, 2,2'-azobis(2-methylpropionamidine)dihydrochloride, produced by Wako Pure Chemicals Industries, Ltd.
-- .: , .. ....
~ ,''.,"'.". ',';', ', '~;
~ , ..... . .
,: .", "
- 23 - ~ ; .
Table-2 .
Properties of finely divided polymer Polymer- Particle Diameter of ization diameter particle Water-stability ~nm) *6 dispersed in resistance .
*5 solvent(nm~*7 *8 1 ~ 69 82 ~
2 ~ 72 82 ~ .
3 ~ 70 85 ~3 :
4 @ 75 86 @ ;
~ 90 98 O :
~ 6 @ 74 80 ~ -x 7 ~ 71 85 @
8 ~ 69 80 ~ - : -9 ~ 80 83 ~
~ 87 93 O :-- 1 O 56 X ' -~ 2 X _ _ _ ~ :
x 3 X _ _ _ .~ 4 C~ 65 X X
X X _ _ 6 ~ 80 350 :` '~ : ::
. .
-! ~
-(NOTE) In Table-2 *5 After polymerization, when the resulting finely divided polymer was filtered through a 100 mesh stainless steel gauze agglomerates remaining on the stainless steel gauze were sufficiently washed with water, then their weights were measured, and the polymerization stability was evaluated by the percent~
age of the resulting weights to the weights of the -charged monomers. When this percentage was a value ~ -mentioned on the left side, below. the polymerization stability was evaluated by the mark described on the right side, below.
less than 0.5%
from 0~5% to 2% : O
from 2S~ to 5% :
more than 5% : x~ -~
A *6 It was measured by Nanosizer N-4 manufactured by Coulter Co. ~ ;
*7 After drying the finely divided polymer at 60C, it was re-dispersed in acetone, and the diameters of - ; ; `~;
particles dispersed in acetone were measured by Nanosizer N-4 manufactured by Coulter Co.
~; *B A polymer film produced on a glass sheet was dipped in water, and the whitened state of the film was evaluated according to the following standard.
After lapse of 1 hours, not whitened at all :
After lapse of 1 hours, slightly whitened : O i -` ~ Whitened in 10-30 minutes :
Immediately whitened : x ~- 30 Herein below, application examples wherein the ~ finely divided gelled polymers obtained according to this `~ invention were applied to cationically electrodepositable paints will be shown.
Application EXAMPLE 1 To 572 parts of a clear emulsion for cationic electrodeposition (tra~en~a~me ~Elecron 9450n, a product of i~
~* -rR
, : .;
. . .
-Kansai Paint Co., Ltd.) comprising a polyamide-modified epoxy resin and a completely blocked diisocyanate having a solids content of 35% were added 75 parts of a dis-persion of the finely divided gelled polymer having a solids content of 20%, a pH of 7 and a viscosity of 90 centipoises obtained in Example 7 and 139.4 parts of the following pigment paste A having a solids content of 43%
with stirring, and the resulting mexture was diluted with 588.5 parts of deionezed water to obtain a cationically -eleCtrodepositable coating.
. . ..
Pigment paste ' '. ' .
A modified epoxy resin 5 Titanium oxide 14 Purified clay 10 Carbon black 1 Deionized water 39.7 Total 69.7 A cationically electrodepositable coating was obtained as in Application Example 1 except that 75 parts 15 of a dispersion of the finely divided gelled polymer -having a solids content of 20%, a PH of 3.8 and a visco-sity of 150 centipoises obtained in Example 8 was used as ;
the finely divided gelled polymer.
A cationically electrodepositable coating was obtained as in Application Example 1 except that 75 parts of a dispersion of the finely divided gelled polymer having a solids content of 20%, a pH of 3.7 and a visco-' sity of 150 centipoises obtained in Comparative Example 4 was used as the finely divided gelled polymer.
A 0.8 x 300 x 90 cm cold-rolled dull steel _ plate (an angle of the edge portion was 45C) chemically A5 ? treated with "Palbond 3030" (a ~ for a product of Nihon Parkerizing Co., Ltd., a zinc phosphate-type) was dipped in each of the cationically electrodepositable ~ -coatings obtained in Application Examples 1 to 3, and electrodeposition-coating was conducted using the above -plate as a cathode. The conditions of an electrodeposi-tion coating bath were that a temperature was 30C, pH
6.5 and a voltage 300 V. An electrodeposition-coated film having the thickness of 20 microns (based on a dry film thickness) was formed, then washed with water and baked at 185C for 20 minutes. The properties of the coated plates weEe measured with the results shown in - ~
Table-3. Moreover, melt viscosities of the coated plates `-- -were also measured and the results are shown in Table-3.
Methods for measuring properties (*9) Melt viscosities of coated films; -The melt viscosity of the electrodeposition- -~
~ coated film in baking is evaluated from a heat flow "~
;~ appearance of a pencil scratch based on the melt visco-sity by a measuring method using a rolling ball (accord- ;
ing to JIS-Z-0237). The value is a minimum viscosity (centipoises).
(*10) Covering property of edge surfaces Electrodeposition coating is conducted on a steel plate having an edge angle of 45DC under such 30 conditions that a thickness of a cured film in a general -~
portion becomes 20 microns, and the coated steel plate is cured under given baking conditions to prepare a test plate. The test plate is put on a salt spray device such -~
that the edge of the test plate is vertical, and then a ~ ~ -35 salt spray test is continued for 168 hours in accordance ~ --with JIS-S-237i. Corrosion resistance of the 45C edge ''. ~ ' ",, .~ .
-~- 1 3301 34 ' portion is evaluated as follows: -~ : Rust does not occur at all O : ~ust slightly oddurs. ~--x : Rust heavily occurs. ;
(*ll)Smoothness of coated surface:
A finishing property of the electrodeposition-coated surface is evaluated by visual observation.
O : Good ~ : Nearly good ~: Slightly bad (*12) Impact resistance:
Measured in an atmosphere of 20C according to JIS K-5400-1979 6, 13, 3B. The value is a maximum height (cm) that does not cause a damage of the coated 15 film under such conditions that a dropped weight is 500g ~
and a diameter of a rear end of an impact center is 1/2 -inch. The maximum value is 50 cm.
(*13) Chipping resistance:
The electrodeposition-coated, baked plate is ~ -~
20 further coated with a thermosetting intermediate coat and a topcoat and heat-cured. The resulting plate is sub- ~ -jected to the following test~
A 1 ) Test device: Q-G-R~graveloveter (a device of Q Panel Company) 2) Stones to be air-blasted: ground stone having a ~ -diameter of 15 to 20 mm 3) Volume of stone to be air-blasted: about 500ml 4) Pressure of a blasting air: about 4 kg/cm2 5) Temperature in test: about 20C
-~- 30 A test piece is fixed on a test piece holding ~ -base, and about 500 ml of ground stones are shot against the test piece at a blasting air pressure of about 4 kg/cm . Thereafter, the condition of the coated surface is evaluated. The condition of the coatd surface is evaluated by visual observation according to the fol-lowing standard.
.
, - ' ~
., ~' ,. - ,~: ' ' , ,. , . ., . -. .. .. - ~ . :, , , ,. - . .
- ~330~34 ~ ~ ~
(good): A flaw due to shooting is slightly -observed on part of the top coat and the electrodeposition-coated film is not peeling off at all. -~ (slightly bad): A flaw due to shooting is observed on the top coat and the intermediate coat, and the electrodeposition-coated film -~
is slightly peeled off.
~ (bad): A flaw due to shooting is heavily observed on the top coat and the inter-mediate coat and the electrodeposition-coated film is notably peeled off.
(*14) Adhasion after dipping in hot water:
~5 After dipping in hot water at 40C for 20 days, i ~-100 squares havimg a size of 1 x 1 mm are provided on the coated film in accordance with JIS X-5400-1797 6.15, and -~
an adhesive cellophane tape is put on the surface. Said tape is abruptly peeled off and the condition of the coated surface is evaluated.
: Good ~ ~Ai : An edge of the crosscut is slightly peeled off. ~
x : Some parts of the 100 squares are peeled off. -~ -~ , . , ~ : , -,, :, ,. - - - . -;; ~'. :.~,.,-,''.:.
-:
. ~ ,, ., ", ,,,,~:.
. . ;:; ' . ~,- -... : :- :; ~
;,,: ~ . . : .
,". ~;'.".'~' ., .. . ' ~.
': , ' - ~ i ' i ,:: . . ' Table-3 Application Example Test items 1 2 3 Melt viscosity of a coated film (*9) 106 1o6 105 surface (*10) _ _ O ~ -Smoothness of a coated ~
surface (*11) ~J O A
Impact resistance (*12) 50 50 50 Chipping resistance (*13) Andhesion after dipping in hot water (*14) ~ _
This invention relates to a finely divided gelled polymer and a process for producing the same. More specifically, this invention relates to a finely divided gelled polymer crosslinked internally obtained by emul-sion polymerization in the presence of a reactive emulsi-fier, a cationically electrodepositable polymer crosslink-ed internally having a hydrolyzable alkoxy silane group and a hydroxyl group, obtained by emulsion polymerization in the presence of a reactive emulsifier, and a process for producing a finely divided gelled polymer excellent in polymerization stability comprising carrying out emulsion polymerization in the presence of a water-soluble azoamide compound as a polymerization initiator.
tPrior art]
Finely divided polymers gelled by crosslinking reactions in the particles and processes for producing such polymers have heretofore been well known. For -example, there have been known a process for emulsion polymerizing a monomeric mixture comprising a monomer for -~
crosslinking containing at least two ethylenic double bonds in an aqueous medium (British Patent No. 967,051 -i ; and European Patent Application No. 259181-A) and a ~ -process for obtaining a polymer comprising dispersion polymerizing a monomeric mixture containing glycidyl (meth)acrylate and (meth)acrylic acid in the presence of ~; a dispersion stabilizer in a non-aqueous medium, and simultaneously, reacting these functional groups (U.S.
Patent 4,025,473). Especially, as processes for produc-ing a polymer in an aqueous medium using an alkoxy silane monomer, there may be cited a process for obtaining a polymer comprising emulsion polymeriaing a mixture of an alkoxy silane monomer with the other monomer in an aqueous medium in the presence of a non-reactive surface active agent (Europen Patent Application No. 153600-A), a -process for obtaining a delustered electrodeposition- -- ~ - . ' : ' ' - ':
.
coated film for aluminum building material which com-prises copolymerizing an alkoxy silane monomer, (meth)-acrylic acid and the other monomer, dispersing the result-ing copolymer in water, and then subjecting the disper sion to electrodeposition coating. (Japanese Laid-Open Patent Publication No, 67396/1984), a water-soluble composition comprising combining an acryl copolymer containing an alkoxy silane group and a carboxyl group with a colloidal silica (Japanese Patent Publication No.
47178/1986) and a process for obtaining a polymer com-prising dispersing an acryl copolymer containig an alkoxy silane group and a cationic group in water and crosslink- -ing the resulting dispersed copolymer in the molecule -(European Patent Application No. 282000-A).
The finely divided gelled polymers obtained by the conventional processes are added to a paint composi- ~ ~
tion, exert influences over the rheological characte- -ristics and physical characteristics of the paint composi- ~ ;
tion, resulting in contributing to the improvements in the spraying effect of the paint, prevention of sagging of the coated film and the pattern control of a metallic pigment. However, many of such finely divided gelled - -polymers are of non-aqueous dispersion, or even if they - -~
are dispersed in aqueous medium, they are dispersions obtained by emulsion polymerization in the presence of a non-reactive surface active agent, and adversely affect various properties of the coated film such as water resistance, solvent resistance and chemical resistance.
On the other hand, cationically electrodeposit- ;
able paints broadly used in various industries centering around the automobile industry has per se excellent rust-inhibiting property, however, the coated film in the edge portion of the object to be coated do not become thick and are inferior in edge covering property. In order to solve this problem, investigations were made in an attempt to apply said finely divided gelled polymer to . ~ , ~ ~330134 the cationically electrodepositable paint. Since the A known finely divided gelled polymers are dispersions of ~-1~ anionic or nonionic or nonionic type, it is usually difficult to apply them to cationically electrodeposit able paint. Even if the known finely divided gelled polymers can be applied to the cationically electrodeposit-able paint, the stability of the electrodeposition coat-ing bath, electrodepositable characteristics, as well as water resistance and corrosion resistance of the coating are impaired. Consequently, a cationically electrodeposit-able paint containing the known finely divided gelled polymers cannot be applied to the practical uses in this field.
The present inventors have made assiduous lS investigations to develop a finely divided gelled polymer which would be useful as a vehicle for a paint, and found as a result that a finely divided gelled polymer cross-linked internally incorporated with a group having a surface activity by chemical bond in the surface of the resin is very effective for solving ~ drawback. This finely divided gelled polymer has a good dispersion stability, and when added to a paint, it is very effective for improving the rheological characteristics and physical characteristics of the paint composition without adversely affecting the various properties of the coated film such as water resistance, solvent resistance and chemical resistance.
Further, the present inventors found that a finely divided gelled polymer crosslinked internally hav- ~ `-ing an alkoxy silane goup, a hydroxyl group and a cationic ; group is useful as a rheology controlling agent of a cationically electrodepositable paint. This polymer has ~
a cationic electrodepositability, does not impair stabil- ~ -ity of the electrodeposition coating bath and electro~
depositable characteristics even when it is added to a cationically electrodepositable paint, does not impair ;~
: ~:, . .
1 330 1 34 ~ -the water resistance, corrosion resistance and smoothness of the surface of the coated film because of crosslinking between particles and crosslinking between the polymer particles with the base resin derived from condensation -, 5 of a silanol group formed by the hydrolysis of alkoxy -- - -silane group with another silanol group and a hydroxyl group at the time of baking , and is very effective for prevention of the cissing and improvement of the edge -~ -cover property, the adhesivility and the chipping resis-10 tance of the cationically electrodeposited coated film. : -And this finding has led us to completion of this inven-tion. -Thus, according to one aspect of this inven- ~ ;
tion, there is provided a finely divided gelled polymer which is obtained by emulsion polymerizing (a) a polymerizable monomer having at least two - --radically polymerizable unsaturated groups in the mole-cule and --(b) a radically polymerizable unsaturated monomer other than the one mentioned in (a) above in the presence of a reactive emulsifier having an allyl group in the molecule. ;
And, according to another aspect of this in-vention, there is provided a process for producing a -finely divided geled polymer excellent in polymerization stability which comprises emulsion polymerizing Z ~;
(a) a polymerizable monomer having at least two -radically polymerizable unsaturated groups and (b) a radically polymerizable unsaturated ~ -monomer other than the one mentioned in (a) above in the presence of a reactive emulsifier having an allyl group in the molecule, characterized by using a water-soluble azoamide compound as a polymerization initiator.
Hereinbelow, a further detailled description will be made with reference to a finely divided gelled polymer and a process for producing the same according to this invention.
In this invention, the monomers constituting the finely divided gelled polymer are (a) a polymerizable monomer having at least two radically polymerizable unsaturated groups in the mole-cule, and (b) a radically polymerizable unsaturated monomer other than the one mentioned in (a) above.
The polymerizable monomer having at least two ~10 radically polymerizable unsaturated groups-rn~~aeF~(a) [hereinafter referred to as "the monomer (a)~] includes a polymerizable un~aturated monocaboxylic acid ester of a polyhydric alcohol, a polymerizable unsaturated alcohol -ester of a polybasic acid and an aromatic monomer substi-tuted with at least two vinyl groups.
Specific examples of the monomer (a) include ethylene glycol diacrylate, ethylene glycol dimetha- ~ - -crylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethac- - ~- -20 rylate, trimethylolpropane triacrylate, trimethylol- - --~
propane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacry-late, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate, glycerol diacrylate, glycerol allyloxy dimethacrylate, l,l,l-trishydroxymethylethane diacrylate, l,l,l-trishydroxy-methylethane triacrylate, l,l,l-trihydroxymethylethane 3Q dimethacrylate, l,l,l-trishydroxymethylethane trimeth- -;;
acrylate, l,l,l-trishydroxymethylpropane diacrylate, l,l,l-trishydroxymethylpropane triacrylate, l,l,l-trishydroxymethylpropane dimethacrylate, l,l,l-trishydroxymethylpropane trimethacrylate, triallyl cyanurate, trially isocyànurate, trially trimellitate, -diallyl terephthalate, diallyl phthalate and divinyl benzene.
~ .: .:. : . . :
'.. ~ '. -~.''' ','; '' ' 1 330 1 34 ~; -,.
- 6 - ;
Of the aforesaid monomers (a), the polymeriz- -able unsaturated monocarboxylic acid ester of a poly-hydric alcohol and the aromatic monomer substituted with at least two vinyl monomers are preferable for this 5 invention. Of these, ethylene glycol di(meth)acrylate, ~ ;
triethylene glycol dimethacrylate, tetraethylene glycol ;
dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate and divinyl benzene are espe- ~ ~ -cially preferable.
_ The radically polymerizable unsaturated monomer A f oaid (b) lhereinafter referred to as "the monomer (b)~] is another half of the monomers constituting the finely divided gelled polymer of this invention, which includes the monomers belonging to the following groups.
A poly~erizable unsaturated vinyl silane ;~
monomer containing a vinylic double bond and a hydro-lyzable alkoxy silane group: -For example, a compound represented by the -20 general formula ; - -R3SiX.
In the formula, X represents a vinylic unsatu-rated group such as gamma-methacryloxypropyl and R re-presents an acetoxy group or an alkoxy group having 1 to 8 carbon atoms. Examples of the alkoxy group include besides methoxy, ethoxy, propoxy, butoxy, isobutoxy, pentoxy and hexoxy; methoxymethoxy, ethoxymethoxy, alkoxyallyloxy and ethoxyphenoxy. The preferable R is a methoxy or ethoxy group.
Typical examples of the monomer include vinyl ~
trimethoxysilane, vinyltriethoxysilane, vinyltris(2- ~ ; -methoxyethoxy)silane, gamma-methacryloxypropyl tri- ;
methoxysilane and vinyl triacetoxysilanes. Of these, the most preferble is gamma-methacryloxypropyl trimethoxy-silane.
A polymerizable unsaturated monomer containing a vinylic double bond and a hydroxyl group: -`~
For example, there may be cited 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, allyl alcohol and methallyl alcohol.
A polymerizable unsaturated monomer containing a carboxyl group:
For example, there may be cited acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid.
A nitrogen-containing alkyl (meth)acrylate monomer For example, there may be cited dimethyl amino~
ethyl (meth)ecrylate.
A polymerizable unsaturated amide monomer: ~ -For example, there may be cited acrylamide ~ -15 methacrylamide, N,N-dimethylacrylamide and N,N-dimethyl- ~ ~;
amino propyl acrylamide.
A polymerizable unsaturated nitrile monomer:
For example, there may be cited acrylonitrile ~ -and methacrylonitrile. ; ~-An alkyl (meth)acrylate monomer;
For example, there may be cited a (Cl-C4) alkyl ester of (meth)acrylic acid such as methyl (meth)- - -~
acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and lauryl (meth)acrylate.
A polymerizable unsaturated glycidyl monomer:
For example, there may be cited glycidyl (meth)- -;~ acrylate, A polymerizable vinyl aromatic monomer:
For example, there may be cited styrene, alpha-~, 30 methyl styrene, vinyl toluene and t-butyl styrene. -~
An alpha-olefin monomer: ~ - ; 'r' ' For example, there may be cited ethylene and propylene. -An aliphatic vinyl ester monomer:
For example, there may be cited vinyl acetate and vinyl propionate.
: -: .
,, ~
. ~ - .: .: :
A diene monomer; ~ ;
For example, there may be cited butadiene and isoprene.
These monomers (b) may be properly selected 5 according to the desired characteristics of the finely -divided gelled polymer and may be used singly or in combination of at least two.
The blending ratio of the monomer (a) and the monomer (b) constituting the finely divided gelled polymer of this invention is within the following range.
The monomer (a): 1 to 99% by weight, preferably 3 to 20~ by weight -The monomer (b): 1 to 99% by weight, preferably 80 to 97% by weight.
Further, in this invention, a cationic finely divided gelled polymer which is especially useful as a rheology controlling agent for a cationic electrodeposit-able paint may be obtained by emulsion polymerizing the aforsaid monomer (a) and the following (b-l), (b-2) and (b-3) monomers selected from the aforesaid monomer (b) as the essential components in the presence of a cationic reactive emulsifier containing an allyl group in the molecule.
b-l) a polymerizable unsaturated vinylsilane monomer containing a vinylic double bond and a hydrolyzable alkoxysilane group~
(b-2) a polymerizable monomer containing a vinylic double bond and a hydroxyl group;
and ~ ~ -~, ~ 30 (b-3) the other polymerizable monomer having no carboxyl group selected from the group ; consisting of a nitrogen-containing alkyl (meth)acrylate monomer, a polymerizable unsaturated amide monomer, a polymer-izable unsaturated nitrile monomer, an alkyl ~meth)acrylate monomer, a polymer-': :
~ . .
^ 1 330 1 34 _ 9 _ izable unsaturated glycidyl monomer, a -~
polymerizable vinyl aromatic monomer, an ;~-~
alpha-olefin monomer, a diene monomer and vinyl ester monomer of a fatty acid.
The blending ratio of the monomer (a) and the (b-l) to (b-3) monomers is within the following range.
The monomer (a): 1 to 30% by weight, preferably 3 to 20% by weight; -~
The monomer ~b-l): 1 to 30% by weight, preferably 3 to 20% by weight;
The monomer (b-2): 1 to 30% by weight, preferably -3 to 20% by weight;
The monomer (b-3): 10 to 97% by weight, preferably 40 to 91% by weight. ~ -lS As the reactive emulsifier containing an allyl group in the molecule used in this invention, the fol~
lowing compounds are included.
A (1) An allYl qrouP-containinq anionic reactive emulsifer;
-~ As typical ones, there may-e-cited a sulfonic acid salt represented by the following general formula 1) or (2) `~ ln-coo~Ao~ncn2-c-cn2 (1) ~:~
CH-COO( AO) nCH2-C-CH
CH-COOR2 (2) ;- ~
;, S03Ml , ~, ,, wherein Rl represents a hydrogen atom or a methyl group, R2 represents a hydrocarbon having a hydrocarbon group or a substituent, or an ; `` --:. :: . . ::~
-~ 1 330 1 34 -- 1 0 -- " "
organic group containing an oxyalkylene group, ; .
A represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, n is 0 or a positive number, M represents an alkali metal or alkaline earth metal, ammonium, an organic amine salt group or an organic quaternary ammonium salt group, and m is a -:
atomic or ionic valence of M;
or a sulfosuccinic acid diester salt represented by the -following general formula 3 or 4 .~
CIH2COO(AO)nRl R12 CHCOO-CH2CHCH20CH2C=CH2 (3) OH
3Ml m CH2CoO-CH2Cl HcH20cH2c CH2 OH
CHCOO(AO)nRl (4) S03Ml m wherein Rl represents a hydrocarbon group optionally :~ having a substituent, a phenyl group, an amino group or a carbocylic acid residue, R2 re-presents a hydrogen atom or a methyl group, A ~.
represents an alkylene group having 2 to 4 carbon atoms, n is an integer of 0 to 100, M - :¦
represents a univalent or divalent cation, and m is an ionic valence of M;
: or a compound represented by the following general formula (5) . ~ ~ -R
~ -O(AO)nSO3M (5) R2 ~ :
1 3 3 0 1 3 4 ! ~ ~
-- 1 1 -- ~ , wherein Rl represents an alkyl, alkenyl or aralkyl - -group having 4 to 1~ carbon atoms, R2 repre-sents a hydrogen atom or an alkyl an alkenyl or ~ ~;
an aralkyl group having a 4 to 18 carbon atoms, A represents an alkylene group having 2 to 4 - -carbon atoms or a substituted alkylene group, n is an integer of 2 to 200 and M represents an -alkali metal atom, NH4 or an alkanolamine residue.
These compounds are known (see, for example, Japanese Patent Publication No. 46291/1974, DE 3317336-A, Japanese Laid-Open Publication No. 221431/1987 and Japanese Laid-Open Patent Publication No. 23725/1988). -' ~hese compounds are commercially available ~ under ther~LJ~ o~ nEliminol JS-2" (Sanyo Chemical - ~
;~ Industries, Ltd.), "Ratemuru S Series~ (Kao Corporation) - - -and ~Aqualon HS Series~ (Dai-ichi Rogyo Seiyaku Co., :
Ltd.).
Of the aforesaid emulsifiens, an anionic re~
~` active emulsifier which is gradually incorporated in the polymer during the polymerization is suitable, and espe-cially so long as it is an anionic reactive emulsifier ; con~aining an allyl group which is a group relatively low ;
in reactivity, it is not limited to what is mentioned above only, but it is included within a broad range. And'`~
the æmount of the anionic reactive emulsifier containin~
thè allyl group used is usually 0.1 to 30% by weight, ;~ preferably 0.5 to 5% by weight per 100 parts by weight of lthe solids content of the finely divided gelled poly-mer.
-~ (2) An allyl group-contalnlng catlonic reactlve emulsifier~
A typical example is a reactive emulsifier having a quaternery ammonium salt represented by the `~ following general formula (6) ~ ~
,' :''.~'` ' ' 1 N CH2-CH-CH2-O-CH2-1=CH (6) ~ :
' wherein Rl represents a hydrocarbon group having 8 to 22 carbon atoms optionally having a substituent, .
R2 and R3 represent an alkyl group having 1 to 3 carbon atoms, R4 represents a hydrogen atom or a methyl group and X~ represents a univalent anion.
This compound is known (see Japanese Laid-Open Patent Publication No. 78947/1985) and is commercially A available under the traden~me of "Ratemuru K-180" (Kao -Corporation).
Of the aforesaid emulsifiers, a cationic re- ..
active emulsifier which is gradually incorpotated in the .
polymer during the polymerization is suitable, and if it is a cationec reactive emulsifier containing an allyl . ~ ::
group which is a group relatively low in reactivity, it is not limited to what is mentioned above only, but -included within a broad range. The amount of the allyl . - :~
20 group-containing cationic reactive emulsifier used is :
usually 0.1 to 30% by weight, preferably 0.5 to 5% by :
weight per 100 parts by weight of the solids content of the finely divided gelled polymer.
~: ~3) An allYl qrouP-containinq nonionic reactive emulsifier:
What is typical of this category is a compound represented by the following general formula (7) CH CH=CH ..
Rl~,~_~
~ O ~-O(AO)nH (7) R ~ :
.
!; `' :. : - , . - ' , ~ . , .. .. , . , . , - : : : . , , :: . ' - . . - ' : . ' , ., - . , . .: . :- : :' ; . . : . . ; -- . ....
1 3 3 0 1 3 4 ! ~ ~
wherein -~
Rl represents an alkyl, alkenyl or aralkyl -~
group having 4 to 18 carbon atoms, R2 represents ; -~
a hydrogen atom, an alkyl group, alkenyl group or aralkyl group having 4 to 18 carbon - atoms, A represents i~ alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and n is an integer of 2 to 200. -This compound is known (see Japanese Laid-Open 10 Patent Publication No. 100502/1087) and commercially available under the trade ~e~of "H-3355N" (Dai-ichi Rogyo Seiyaku Co., Ltd.), Of the aforesaid emulsifiers, a nonionic reac-tive emulsifier which is gradually incorporated in the 15 polymer during the polymerization is suitable, and if it ~- --is a nonionic reactive emulsifier containing an allyl group which is a group relatively low in reactivity, the emulsifier is not limited to what is mentioned above only, but is included within a broad range. In addition, -20 this nonionic reactive emulsifier may be blended at an -optional ratio with the anionic reactive emulsifier or ~-the cationic reactive emulsifier, and the blending ratio -is properly selected according to the desired characte~
ristics of the finely divided gelled polymer. `;~
~he amount of the mixture of the anionic re- ~ - ~
active emulsifier or the cationic reactive emulsifier -~ -with the nonionic reactive emulsifier used is usually 0.1 to 30% by weight, preferably 0.5 to 5% by weight per 100 parts by weight of the solids content of the finely - -30 divided gelled polymer. ` ~ ~ `
As a polymerization initiator used in this~ -~
invention, a water-soluble azoamide compound represented by the following general formula (8) .: . .. .: ..
IH3 ICH3 ;~
HO-X-NH-C-C-N-N-C - C-NH-X-OH (81 ~ .
Il I I ... ,'' :'. ''.
.`';.'''"'''- ' "' -. ...
wherein X represents a linear-chain or branched-chain alkylene group having 2 to 12 carbon atoms, or represented by the following general formula t9) - -X CH2 7H3 ICH3 I H2X :.
X CH2-C-HN - C-C-N=N - C - C_NH_C_CH2X (9) wherein at least one of Xl, X2, X3 represents a hydroxyl group and the remaining represents a hydrogen atom, is especially suitable.
_ This compound is known (see Japanese Laid-Open A Patent Publications Nos. 218618/1986 and 63643/1986) and is commercially available under the trade namo of "VA
Series" (Wako Pure Chemicals Industries, Ltd,).
The amount of the polymerization initiator may be usually within the range of 0.1 to 1.5 parts by weight per 100 parts by weight of the solids content of the finely divided gelled polymer.
Copolymerization of the unsaturated monomers 20 (a) and (b) may be carried out by the known process for ;
emulsion polymerization, viz. a process for producing an -acryl copolymer. A mixture of the monomers may be re-acted in the presence of a polymerization initiator of a water-soluble azoamide com2ound at a reaction temperature of usually about 50C to about 100C, preferably about ` 80C to about 95C for about 1 to about 20 hours, -The finely divided gelled polymer of this invention has a solids resin content of usually about 10 to about 40% by weight based on the total amount of its aqueous dispersion. The particle diameter of the finely divided gelled polymer is less than 500 nm, preferably 10 to 300 nm, more preferably 50 to 100 nm. The particle ~ `
diameter can be adjusted by adjusting the amount and/or the ratio of the amount of the reactive emulsifier having an allyl group in the molecule, and a finely divided gelled polymer having a particle diameter within the desired range can be easily obtained.
The finely divided gelled polymer of this invention is characterized in that the degree of cross-linking and the hardness thereof can be optionally control-led. When the hardness is low, by air drying, the parti-cles are mutually fused to form a continuous coated film,whereby the coated film large in the initial modudlus and rich in flexibility can be formed. And when the hardhess ; -and the crosslinking density become high, the trans-parency of the polymer film deteriorates, and many streaks and cracks are brought about, but it i8 possible to form a uniform, flat coated film by the joint use of a `
A coalescing agent or ra~i~sin~ ~he drying temperature.
The finely ~YnrhhK~gelled polymer of this invention can be used per se as a vehicle of an emulsion 20 paint that forms a coated film. Further, since it possess- ~ -es hydroxyl groups effectively introduced into the polymer by chemical bonding from a water-soluble azoamide compound which is used as a polymerization initiator, the polymer `~
may also be used as a material for an aqueous baking ~-~ :~
25 paint to be baked and hardened in admixture with an ~ --aminoplast resin such as methylolated melamine resin.
And, when the finely divided gelled polymer is -powderized and added to a powder paint, the polymer -~
particles are useful for improving the blocking property ; -30 and the physical properties of the coated film, and in : -addition, when dispersed in an aqueous solvent, it re- -mains as primary particle and is less viscous. According-ly, it is useful as a material for a high-solid type paint as well. ~esides, it is possible to mix the polymer 35 with the solvent type paint, water-soluble paint and ~-emulsion paint and use it for improving the properties of such paints.
A cationically electrodepositable finely divid-ed gelled polymer obtained by this invention, when added to ordinary cationecally electrodepositable paint and co-electrodeposited, does not bring about such problems as agglomeration, abno~mal electrodeposition and sedimen-tation, and plays a role of a flow controller at the time when the electrodeposited coated film is thermally harde-ned, and exhibits an excellent cissing inhibiting effectand the edge covering effect. Again, the coated film forms a microseparating structure and brings about a large improving effect of the physical properties of the coated film.
~he reason why the finely divided gelled polymer is stably produced by the emulsion polymerization process ~ of this invention is not necessarily c~ear at this point A Of timing. However, it is ~ sler ~ sttributable to the bec~ c~s~ ¢o~O c,~ d fact that bccouso-a water-soluble azoamide ~ompount-used 20 as a polymerization initiatior is a very useful polymer- ~ -~
ization initiator for an emulsion polymerization at a relatively high-temperature, even under the polymeriation conditions at a relatively high temperature of from about 80C to about 95C, the coagulation of th$ produced finely divided gelled polymers is ingibitcd, and that a grou~ having a surface activity is incorporated in the pos60foaionl0f hydroxyl groups effectively introduced to the surface of the polymer by chemical bonding, and that due to thc pPo33c~sion of hydroxyl groups effectively introduced to the surface of the polymer by chemical bonding from water-soluble azoamide compound as the polymerization initiator, the affinity of the polymer with water which is a continuous phase is very good, which enables the polymer to be stably present in water.
The following examples will more specifically illustrate this invention. All parts and percentages appearing in the following examples are by weight.
EXAMPLES 1 to 10 A 1-liter flask o~uppo~ with a stirrer, a thermometer, a condensing pipe and a heating mantle was -charged with deionized water in amounts shown in Table-l and the emulsifiers shown in Table-l in amounts shown in Table-l, and the contents were heated with stirring to 90C, to which 20% of aqueous solutions of 12.5 parts of -the polymerization initiator shown in Table-l dissolved in 500 parts of deionized water was added. After 15 minutes since the addition, 5% of the monomeric m~cture shown in Table-l was added. Then, after further stirring for 30 minutes, the remaining monomeric mixtures and the polymerization initiator began to be added dropwise. The - -monomeric mixtures and the polymerization initiators were - -~
15 added dropwise over 3 hours and 3.5 hours, respectively. - -~
During the period, the polym~rization temperature was -- -maintained at 90C. After dropping of the aqueous solu-tions of the polymerization initiators, heating~ Y~
continued for 30 minutes to maintain the temperature at ~ ` -90C, then the temperature was lowered to room tempera-ture. The resulting polymers were taken out using a ~
filter cloth ~ obtain finely divided gelled polymers ~ - -having the solids content of 20%. The properties of the -resulting polymers are shown in Table-2. ~
COMPARATIVE EXAMPLE 1 - `
Example 1 was repeated except that the charged ~ -contents of the l-liter flask were changed to 3543.1 parts of deionized water and 44.4 parts of an anionic ~ `
reactive emulsifier of "Newcol 271A" (trade namc Nippon Nyukazai Co., Ltd., a 45% aqueous solution) to obtain a finely divided gelled polymer having the pro-perties shown in Table-2. ~ -;
When emulsion polymerization was carried out as in Example 1, except that the charged contents of the l-liter flask w changed to 3567.5 parts of deionized water and 20 parts of an anionic vinylic reactive emul-sifier of sodium p-styrenesulfonate, while the monomers werer being added dropwise, the system agglomerated and a finely devided gelled polymer was not obtained.
When emulsion polymerization was carried out as in Example 1 except that the charged contents of the l-liter flask were changed to 3567.5 parts of deionized water and 20 parts of an oligoester acrylate type anionic reactive emulsifier of "Newfrontire A-229E" (trade name 10 ~ Dai-ichi Kogyo Seiyaku Co., Ltd.), while the monomers were being added dropwise, the system agglomerated and a finely divided gelled polymer was not obtained.
According to the same prescription as in Ex-15 ample 7 except that the charged contents of the l-liter flask were changed to 3555.8 parts of deionized water and a cationic non-rçactive emulsifier of "Kotamine 86P Conc~ `
(tradc~m~ of stearyl trimethyl ammonium chloride of Kao Corporation, a 63~ aqueous solution), a finely divided 20 gelled polymer having properties shown in Table-2 was obtained.
When emulsion polymerization was carried out according to the same prescription as in Example 7 except -25 that the polymerization initiaor was changed to a water-soluble azodiamidine compound of ~V-50" (2,2'-axobis(2-methylpropionamidine)dihydrochloride, a product of Wako -~
;- ~ Pure Chemicals Industries, Ltd.), while the monomers were --being added dropwise, the system agglomerated, and a ~ ``-, 30 finely divided gelled polymer was not obtained.
; COMPARATIVE EXAMPLE 6 ~ f ; According to the same prescription as in Example 6 except that the following mixture of monomers was used as the monomeric mixture, a finely divided gelled polymer 35 having properties shown in Table-2 was obtained. ~ -Styrene 500 parts n-Butyl acrylate 500 parts ~ 3301 34 -- 1 9 , Table-l .
¦Amount of ¦initially Emulsifier Icharged deionized -\ water Kind *1 Amount *2 (parts) used (parts) __ ,' . ,' ' . .
1 3536.5 JS-2 51(20) 2 3547.5 S-120A 40(20) 3 3547.5 S-120A 40(20) 4 3567.5 HS-10 20(20) 3557.5 S-120A/H-3355N 20/10(10/10) 6 3507.5 R-180 80(20) 7 3507.5 K-180 80(20) ;
8 3507.5 X-180 80(20) -9 3517.5 X-180 120(30) 3562.5 K-180/H-3355N 60/15(15/15) 1 3543.1 N-271A 44.4(20) 2 3567.5 Sodium p-styrenesulfonate 20(20) ~-~ 3 3567.5 A-229E 20(20) .~4 3555.8 86P 31.7(20) 3507.5 X-180 80(20) 6 3507.5 K-180 80(20) - to be continued -~ 133013~ ~
Table-l (continued) Monomer Kind of polymeri-Cbmposition *3 Amount zation used (parts) *4 1 St/nBA/1.6-HDDA 470/470/60 VA-086 2 St/nEA/1,6-HDDA 470/470/60 VA-086 3 St/nBAJl,6-HDDAv~Ea/MoaC 450/450/60/20/20 VA-086 4 St/neA~1,6-HDDA 470/470/60 VA-086 5 St/nBA/1,6-HDDA 470/470/60 VA-086 ~ 6 St/nBA/1,6-HDDA 470/470/60 VA-086 X 7 St/nB~/1,6-HDDA/HEP/K~M-503 430/440/40/40/50 VA-086 8 St/ne~/1,6-~HDDA/bEa/YæX-503 430/440/40/40/50 VA-080 9 MM~/nB~/1,6-HDDA 470/470/60 VA-086 O MM~nB~/1,6-HDDA 470/470/60 VA-086 1 St/nB~/l,6-HDDA 470/470/60 VA-086 X 2 St/nEA41,6-HDDA 470/470/60 VA-086 P 3 St/nBA/1,6-HDDA 470/470/60 VA-086 4 St/nBA/1,6-HDDAvHEa/Y~M-503 430/440/40/40/50 VA-086 5 St/n2~/1,6-HDDAvEEAv~M-503 430/440/40/40/50 V-50 6 St/nB~ 50/50 VA-086 .'.'~ ~ '' '.-.~
(NOTE) in Table-l *1 JS-2: An allyl group-containing anionic r~actdive A emulsifier of a sulfosuccinic acid type ~ ~ -"Eleminol JS-2" of Sanyo Chemical Industries, Ltd., a 39% aqueous solution), S-120A: an allyl group-containing anionic reactive emulsifier of a sulfo-succinic acid type (t ~ namc "Ratemuru S-120A of Xao Corporation, a 50% aqueous solution), HS-10: an ;
allyl group-containing anionic reactive emulsifier of a sulfonic acid type (trade ~ 'Aqualon HS-10"
of Dai-ichi Kogyo Seiyaku Co., Ltd., a 100% net -;
product), H-3355N: an allyl group-containing nonio-nic reactive emulsifier (a product of Dai-ichi Kogyo Seiyaku Co., Ltd., a 100% net produc ~ , K-180: an allyl group-containing cationic reactive emulsifier of a quaternary ammonium salt type (trade ~
"Ratemuru K-180" of Kao Corporation, a 25% aqueous solution, N-271A: an anionic non-reactive emulsifier of a sulfonic acid type ~trr~4ddcen~mmcr~nNewcol 271A f Nippon Nykazai Co., Ltd., a 45% aqueous solution), A-229E: an anionic reactive emulsifier of an oligo-ester acrylate type (trade n~mP "Newfrontier A-229E, -a 100% net product). --*2 Numerals inside the brackets show the amounts used calculated as the solids contents.
*3 St; styrene, n-BA; n-butyl acrylate, 1,6-HDDA;
1,6-hexanediol diacrylate, HEA; 2-hydroxyethyl acrylate, MAAc; methacrylic acid, KBM-503; gamma-methacryloxypropyltrimethoxy silane, procuced by Shin-Etsu Chemical Co., Ltd. and is commercially available, MMA; me~hyl methacrylate. -;~
s~
*4 VA-086; a water-*e~ ~ ~azoamide polymerization initiator: 2,2'-azobis[2~methyl-N-(2-hydroxyethyl)-propionamide] produced by Wako Pure Chemicals Industries, Ltd. and is commercialy available, VA-080; a water-soluble azoamide polymerization initiator; 2,2'-azobis{2-methyl-N-[l,l-bis-thydroxymethyl)-2-hydroxyethyl3propionamide}, pro-duced by Wako Pure Chemicals Industries, Ltd., V-50 a water-soluble azoamidine polymerization initiator, 2,2'-azobis(2-methylpropionamidine)dihydrochloride, produced by Wako Pure Chemicals Industries, Ltd.
-- .: , .. ....
~ ,''.,"'.". ',';', ', '~;
~ , ..... . .
,: .", "
- 23 - ~ ; .
Table-2 .
Properties of finely divided polymer Polymer- Particle Diameter of ization diameter particle Water-stability ~nm) *6 dispersed in resistance .
*5 solvent(nm~*7 *8 1 ~ 69 82 ~
2 ~ 72 82 ~ .
3 ~ 70 85 ~3 :
4 @ 75 86 @ ;
~ 90 98 O :
~ 6 @ 74 80 ~ -x 7 ~ 71 85 @
8 ~ 69 80 ~ - : -9 ~ 80 83 ~
~ 87 93 O :-- 1 O 56 X ' -~ 2 X _ _ _ ~ :
x 3 X _ _ _ .~ 4 C~ 65 X X
X X _ _ 6 ~ 80 350 :` '~ : ::
. .
-! ~
-(NOTE) In Table-2 *5 After polymerization, when the resulting finely divided polymer was filtered through a 100 mesh stainless steel gauze agglomerates remaining on the stainless steel gauze were sufficiently washed with water, then their weights were measured, and the polymerization stability was evaluated by the percent~
age of the resulting weights to the weights of the -charged monomers. When this percentage was a value ~ -mentioned on the left side, below. the polymerization stability was evaluated by the mark described on the right side, below.
less than 0.5%
from 0~5% to 2% : O
from 2S~ to 5% :
more than 5% : x~ -~
A *6 It was measured by Nanosizer N-4 manufactured by Coulter Co. ~ ;
*7 After drying the finely divided polymer at 60C, it was re-dispersed in acetone, and the diameters of - ; ; `~;
particles dispersed in acetone were measured by Nanosizer N-4 manufactured by Coulter Co.
~; *B A polymer film produced on a glass sheet was dipped in water, and the whitened state of the film was evaluated according to the following standard.
After lapse of 1 hours, not whitened at all :
After lapse of 1 hours, slightly whitened : O i -` ~ Whitened in 10-30 minutes :
Immediately whitened : x ~- 30 Herein below, application examples wherein the ~ finely divided gelled polymers obtained according to this `~ invention were applied to cationically electrodepositable paints will be shown.
Application EXAMPLE 1 To 572 parts of a clear emulsion for cationic electrodeposition (tra~en~a~me ~Elecron 9450n, a product of i~
~* -rR
, : .;
. . .
-Kansai Paint Co., Ltd.) comprising a polyamide-modified epoxy resin and a completely blocked diisocyanate having a solids content of 35% were added 75 parts of a dis-persion of the finely divided gelled polymer having a solids content of 20%, a pH of 7 and a viscosity of 90 centipoises obtained in Example 7 and 139.4 parts of the following pigment paste A having a solids content of 43%
with stirring, and the resulting mexture was diluted with 588.5 parts of deionezed water to obtain a cationically -eleCtrodepositable coating.
. . ..
Pigment paste ' '. ' .
A modified epoxy resin 5 Titanium oxide 14 Purified clay 10 Carbon black 1 Deionized water 39.7 Total 69.7 A cationically electrodepositable coating was obtained as in Application Example 1 except that 75 parts 15 of a dispersion of the finely divided gelled polymer -having a solids content of 20%, a PH of 3.8 and a visco-sity of 150 centipoises obtained in Example 8 was used as ;
the finely divided gelled polymer.
A cationically electrodepositable coating was obtained as in Application Example 1 except that 75 parts of a dispersion of the finely divided gelled polymer having a solids content of 20%, a pH of 3.7 and a visco-' sity of 150 centipoises obtained in Comparative Example 4 was used as the finely divided gelled polymer.
A 0.8 x 300 x 90 cm cold-rolled dull steel _ plate (an angle of the edge portion was 45C) chemically A5 ? treated with "Palbond 3030" (a ~ for a product of Nihon Parkerizing Co., Ltd., a zinc phosphate-type) was dipped in each of the cationically electrodepositable ~ -coatings obtained in Application Examples 1 to 3, and electrodeposition-coating was conducted using the above -plate as a cathode. The conditions of an electrodeposi-tion coating bath were that a temperature was 30C, pH
6.5 and a voltage 300 V. An electrodeposition-coated film having the thickness of 20 microns (based on a dry film thickness) was formed, then washed with water and baked at 185C for 20 minutes. The properties of the coated plates weEe measured with the results shown in - ~
Table-3. Moreover, melt viscosities of the coated plates `-- -were also measured and the results are shown in Table-3.
Methods for measuring properties (*9) Melt viscosities of coated films; -The melt viscosity of the electrodeposition- -~
~ coated film in baking is evaluated from a heat flow "~
;~ appearance of a pencil scratch based on the melt visco-sity by a measuring method using a rolling ball (accord- ;
ing to JIS-Z-0237). The value is a minimum viscosity (centipoises).
(*10) Covering property of edge surfaces Electrodeposition coating is conducted on a steel plate having an edge angle of 45DC under such 30 conditions that a thickness of a cured film in a general -~
portion becomes 20 microns, and the coated steel plate is cured under given baking conditions to prepare a test plate. The test plate is put on a salt spray device such -~
that the edge of the test plate is vertical, and then a ~ ~ -35 salt spray test is continued for 168 hours in accordance ~ --with JIS-S-237i. Corrosion resistance of the 45C edge ''. ~ ' ",, .~ .
-~- 1 3301 34 ' portion is evaluated as follows: -~ : Rust does not occur at all O : ~ust slightly oddurs. ~--x : Rust heavily occurs. ;
(*ll)Smoothness of coated surface:
A finishing property of the electrodeposition-coated surface is evaluated by visual observation.
O : Good ~ : Nearly good ~: Slightly bad (*12) Impact resistance:
Measured in an atmosphere of 20C according to JIS K-5400-1979 6, 13, 3B. The value is a maximum height (cm) that does not cause a damage of the coated 15 film under such conditions that a dropped weight is 500g ~
and a diameter of a rear end of an impact center is 1/2 -inch. The maximum value is 50 cm.
(*13) Chipping resistance:
The electrodeposition-coated, baked plate is ~ -~
20 further coated with a thermosetting intermediate coat and a topcoat and heat-cured. The resulting plate is sub- ~ -jected to the following test~
A 1 ) Test device: Q-G-R~graveloveter (a device of Q Panel Company) 2) Stones to be air-blasted: ground stone having a ~ -diameter of 15 to 20 mm 3) Volume of stone to be air-blasted: about 500ml 4) Pressure of a blasting air: about 4 kg/cm2 5) Temperature in test: about 20C
-~- 30 A test piece is fixed on a test piece holding ~ -base, and about 500 ml of ground stones are shot against the test piece at a blasting air pressure of about 4 kg/cm . Thereafter, the condition of the coated surface is evaluated. The condition of the coatd surface is evaluated by visual observation according to the fol-lowing standard.
.
, - ' ~
., ~' ,. - ,~: ' ' , ,. , . ., . -. .. .. - ~ . :, , , ,. - . .
- ~330~34 ~ ~ ~
(good): A flaw due to shooting is slightly -observed on part of the top coat and the electrodeposition-coated film is not peeling off at all. -~ (slightly bad): A flaw due to shooting is observed on the top coat and the intermediate coat, and the electrodeposition-coated film -~
is slightly peeled off.
~ (bad): A flaw due to shooting is heavily observed on the top coat and the inter-mediate coat and the electrodeposition-coated film is notably peeled off.
(*14) Adhasion after dipping in hot water:
~5 After dipping in hot water at 40C for 20 days, i ~-100 squares havimg a size of 1 x 1 mm are provided on the coated film in accordance with JIS X-5400-1797 6.15, and -~
an adhesive cellophane tape is put on the surface. Said tape is abruptly peeled off and the condition of the coated surface is evaluated.
: Good ~ ~Ai : An edge of the crosscut is slightly peeled off. ~
x : Some parts of the 100 squares are peeled off. -~ -~ , . , ~ : , -,, :, ,. - - - . -;; ~'. :.~,.,-,''.:.
-:
. ~ ,, ., ", ,,,,~:.
. . ;:; ' . ~,- -... : :- :; ~
;,,: ~ . . : .
,". ~;'.".'~' ., .. . ' ~.
': , ' - ~ i ' i ,:: . . ' Table-3 Application Example Test items 1 2 3 Melt viscosity of a coated film (*9) 106 1o6 105 surface (*10) _ _ O ~ -Smoothness of a coated ~
surface (*11) ~J O A
Impact resistance (*12) 50 50 50 Chipping resistance (*13) Andhesion after dipping in hot water (*14) ~ _
Claims (20)
1. A finely divided gelled polymer obtained by emulsion polymerizing (a) a polymerizable monomer containing at least two radically polymerizable unsaturated groups in the molecule, and (b) a radically polymerizable unsaturated monomer other than the one mentioned in (a) above in the presence of a reactive emulsifier containing an allyl group in the molecule.
2. The finely divided gelled polymer of claim 1 wherein said monomer (a) is selected from the group consisting of a poly-merizable unsaturated monocarboxylic acid ester of a polyhydric alcohol, a polymerizable unsaturated alcohol ester of a polybasic acid and an aromatic monomer substituted by at least two vinyl groups.
3. The finely divided gelled polymer of claim 1 wherein said monomer (a) is a polymerizable unsaturated monocarboxylic acid ester of a polyhydric alcohol.
4. The finely divided gelled polymer of claim 2 wherein said monomer (a) is at least one member selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethyleneglycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate and divinyl benzene.
5. The finely divided gelled polymer of claim 1, 2, 3 or 4, wherein said monomer (b) is selected from the group consisting of a carboxyl group containing polymerizable unsaturated monomer, an alkyl ester monomer of (meth)acrylic acid, a polymerizable unsat-urated nitrile monomer and a polymerizable vinyl aromatic monomer.
6. The finely divided gelled polymer of claim 5 wherein said monomer (b) is selected from the group consisting of methyl-(meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate and styrene.
7. The finely divided gelled polymer of claim 1, 2, 3 or 4, wherein the blending ratio of said monomer (a)/said monomer (b) is 1/99 to 99/1 by weight ratio.
8. The finely divided gelled polymer of claim 7 wherein the blending ratio of said monomer (a)/said monomer(b) is 3/97 to 20/80 by weight ratio.
9. The finely divided gelled polymer of claim 1, 2, 3 or 4, wherein said allyl group-containing reactive emulsifier is an ani-onic emulsifier, a cationic emulsifier or a mixture of the anionic emulsifier or the cationic emulsifier with a nonionic emulsifier.
10. The finely divided gelled polymer of claim 1, 2, 3 or 4, wherein said allyl group-containing reactive emulsifier is used in an amount with the range of 0.1 to 30% by weight per 100 parts by 31a weight of the solids content of said finely divided gelled poly-mer.
11. The finely divided gelled polymer of claim 1 obtained by emulsion polymerizing (a) a polymerizable monomer containing at least two radically polymerizable unsaturated groups in the molecule, (b) a radically polymerizable unsaturated monomer con-sisting of (b-1) a polymerizable monomer containing a vinylic double bond and a hydrolyzable alkoxy silane group in the mole-cule, (b-2) a polymerizable monomer containing a vinylic double bond and a hydroxyl group, and (b-3) the other polymerizable monomer having no car-boxylic group selected from the group consisting of a nitrogen-containing alkyl(meth)acrylate monomer, a polymerizable unsatur-ated amide monomer, a polymerizable unsaturated nitrile monomer, an alkyl (meth)acrylate monomer, a polymerizable unsaturated glycidyl monomer, a polymerizable vinyl aromatic monomer, an alpha-olefin monomer, a diene monomer and a vinyl ester monomer of fatty acid in the presence of a cationic reactive emulsifier contai-ning an allylgroup in the molecule.
12. The finely divided gelled polymer of claim 11 wherein the blending ratio of said monomer (a), said monomers (b-1), (b-2) and (b-3) is within the following range on the basis of weight.
the monomer (a) 1 to 30%
the monomer (b-1) 1 to 30%
the monomer (b-2) 1 to 30%, and the monomer (b-3) 10 to 97%.
the monomer (a) 1 to 30%
the monomer (b-1) 1 to 30%
the monomer (b-2) 1 to 30%, and the monomer (b-3) 10 to 97%.
13. A process for producing a finely divided gelled polymer which comprises emulsion polymerizing (a) a polymerizable monomer containing at least two radically polymerizable unsaturated groups in the molecule, and (b) a radically polymerizable undsaturated monomer other than the one mentioned in (a), above in the presence of a reactive emulsifier containing an allyl group in the molecule, characterized by using a water-soluble azoamide compound as a polymerization initiator.
14. The process of claim 13 wherein said water-soluble azoamide compound is a compound represented by the following general formula wherein X represents a straight-chain or branched-chain alkylene group having 2 to 12 carbon atoms or a compound represented by the following general gormula wherein at least on of X1, X2 and X3 represents a hydroxyl group, and the remaining one or ones represent a hydrogen atom.
15. The process of claim 13 wherein said water-soluble assumed compound is used in an amount of 0.1 to 1.5 parts by weight per 100 parts by weight of the solids content of said finely divided gelled polymer.
16. The process of claim 13, 14 or 15, wherein said monomer (a) is selected from the group consisting of a polymerizable unsaturated monocarboxylic acid ester of a polyhydric alcohol, a polymerizable unsaturated alcohol ester of a polybasic acid and an aromatic monomer substituted by at least two vinyl groups; wherein said monomer (b) is selected from the group consisting of a carboxylic group containing polymerizable unsaturated monomer, an alkyl ester monomer of (meth)acrylic acid, a polymerizable unsaturated nitrile monomer and a polymerizable vinyl aromatic monomer; and wherein the blending ratio of said monomer (a)/said monomer (b) is 1/99 to 99/1 by weight ratio.
17. A finely divided gelled polymer obtained by the process of claim 14.
18. A powder obtained by drying the finely divided gelled polymer obtained by emulsion polymerization according to claim 1, 2, 3, 4, 11, 12, 13, 14 or 15.
19. A cationic electrodepositable paint, which comprises:
the finely divided gelled polymer in an emulsion form obtained by emulsion polymerization according to claim 1, 2, 3, 4, 11, 12, 13, 14 or 15, as a vehicle, and an emulsion of a resin suitable for a cationic electrodeposition paint.
the finely divided gelled polymer in an emulsion form obtained by emulsion polymerization according to claim 1, 2, 3, 4, 11, 12, 13, 14 or 15, as a vehicle, and an emulsion of a resin suitable for a cationic electrodeposition paint.
20. The cationic electrodepositable paint of claim 19, wherein the emulsion of a resin suitable for a cationic electrodeposition comprises a polyamide modified epoxy resin and a blocked diisocyanate.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP197,056/88 | 1988-08-09 | ||
| JP19705688A JPH0676568B2 (en) | 1988-08-09 | 1988-08-09 | Process for producing cationic electrodepositable gelled fine particle polymer and cationic electrodeposition coating composition containing the polymer |
| JP197,055/88 | 1988-08-09 | ||
| JP63197055A JP2728443B2 (en) | 1988-08-09 | 1988-08-09 | Method for producing aqueous dispersion of gelled fine particle polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1330134C true CA1330134C (en) | 1994-06-07 |
Family
ID=26510142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000607733A Expired - Lifetime CA1330134C (en) | 1988-08-09 | 1989-08-08 | Finely divided gelled polymer and process for producing the same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5021530A (en) |
| CA (1) | CA1330134C (en) |
| DE (1) | DE3926326C2 (en) |
| GB (1) | GB2221689B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU631586B2 (en) * | 1988-12-19 | 1992-12-03 | 3M Espe Ag | Dental compounds which contain bifunctional acrylic-acid esters or methacrylic-acid esters |
| US5583164A (en) * | 1988-12-19 | 1996-12-10 | Espe Stiftung & Co. Produktions-Und Vertriebs Kg | Dental compositions comprising bifunctional or polyfunctional acrylic-acid esters or methacrylic-acid esters |
| US5348998A (en) * | 1989-08-04 | 1994-09-20 | Kansai Paint Co., Ltd. | Coating composition comprising particles of an emulsion polymerized gelled polymer |
| JPH03215575A (en) * | 1990-01-20 | 1991-09-20 | Kansai Paint Co Ltd | Resin composition for cationic electrodeposition coating |
| JPH03239770A (en) * | 1990-02-16 | 1991-10-25 | Kansai Paint Co Ltd | Resin composition for cationic electrodeposition coating |
| GB2249551B (en) * | 1990-09-28 | 1995-03-08 | Kansai Paint Co Ltd | Cationically electrodepositable finely divided gelled polymers and processes for producing the same |
| US5380781A (en) * | 1992-07-27 | 1995-01-10 | Kansai Paint Co., Ltd. | Cationically electrodepositable fine particles derived from alkoxysilane-modified epoxy resins and cationic electrodeposition paint composition comprising the same |
| GB2303632B (en) * | 1995-07-24 | 1999-03-10 | Toagosei Co Limited | Curable emulsion and coating material comprising the same |
| DE69717734T2 (en) * | 1996-02-23 | 2003-10-16 | Arakawa Kagaku Kogyo K.K., Osaka | AQUEOUS DISPERSION OF CATIONIC PARTICULAR GEL AND METHOD FOR THE PRODUCTION THEREOF |
| JP4389315B2 (en) * | 1999-12-28 | 2009-12-24 | Ｊｓｒ株式会社 | Reactive particles, curable composition containing the same, and cured product |
| JP4822479B2 (en) | 2000-02-18 | 2011-11-24 | 関西ペイント株式会社 | Cationic electrodeposition coating composition |
| US7030066B1 (en) | 2001-11-12 | 2006-04-18 | Charles Piskoti | Wetting composition for high temperature metal surfaces, and method of making the same |
| US20060131543A1 (en) * | 2003-04-10 | 2006-06-22 | Hideki Iijima | Polyaddition product and cationic electrodeposition coating comprising said polyaddition product |
| US20060009593A1 (en) * | 2004-07-08 | 2006-01-12 | Hideki Iijima | Polyaddition compound and cationic electrodeposition paint which contains polyaddition compound |
| US20070015873A1 (en) * | 2005-07-13 | 2007-01-18 | Fenn David R | Electrodepositable aqueous resinous dispersions and methods for their preparation |
| FR2896248B1 (en) * | 2006-01-18 | 2008-03-07 | Arkema Sa | PROCESS FOR THE PREPARATION OF STABILIZED LATEX BY EMULSION POLYMERIZATION |
| US9598588B2 (en) | 2012-05-16 | 2017-03-21 | Ppg Industries Ohio, Inc. | Cationic electrodepositable coating compositions capable of forming low gloss coatings |
| US9505937B2 (en) | 2012-05-16 | 2016-11-29 | Ppg Industries Ohio, Inc. | Anionic electrodepositable coating compositions capable of forming low gloss coatings |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU696029A1 (en) * | 1977-04-11 | 1979-11-05 | Воронежский филиал Всесоюзного научно-исследовательского института синтетического каучука им. академика С.В.Лебедева | Method of preparing synthetic rubber |
| US4151146A (en) * | 1977-12-01 | 1979-04-24 | Celanese Corporation | Process for preparing multifunctional acrylate-modified vinyl ester-alkyl acrylate/methacrylate copolymer coagulum-free latex |
| US4150210A (en) * | 1978-06-19 | 1979-04-17 | Stauffer Chemical Company | Emulsion polymerization of vinyl chloride polymers using mixed emulsifier system |
| JPS58208345A (en) * | 1982-05-31 | 1983-12-05 | Mitsubishi Rayon Co Ltd | Impact-resistant methacrylate resin composition |
| US4514552A (en) * | 1984-08-23 | 1985-04-30 | Desoto, Inc. | Alkali soluble latex thickeners |
| JPS6215202A (en) * | 1985-07-15 | 1987-01-23 | Sanyo Chem Ind Ltd | Reactive emulsifying agent |
| JPS6312334A (en) * | 1986-06-20 | 1988-01-19 | Dai Ichi Kogyo Seiyaku Co Ltd | Emulsifying agent for aqueous resin dispersion |
| JPS6391130A (en) * | 1986-10-06 | 1988-04-21 | Nippon Shokubai Kagaku Kogyo Co Ltd | Reactive surfactant |
| JP2608726B2 (en) * | 1987-07-29 | 1997-05-14 | 第一工業製薬株式会社 | Emulsifier for emulsion polymerization |
-
1989
- 1989-08-08 CA CA000607733A patent/CA1330134C/en not_active Expired - Lifetime
- 1989-08-08 US US07/390,876 patent/US5021530A/en not_active Expired - Lifetime
- 1989-08-09 DE DE3926326A patent/DE3926326C2/en not_active Expired - Lifetime
- 1989-08-09 GB GB8918169A patent/GB2221689B/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3926326C2 (en) | 1994-12-01 |
| GB8918169D0 (en) | 1989-09-20 |
| GB2221689A (en) | 1990-02-14 |
| DE3926326A1 (en) | 1990-02-15 |
| GB2221689B (en) | 1992-04-22 |
| US5021530A (en) | 1991-06-04 |
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